Adsorption-induced structural changes of gold cations from two- to three-dimensions
Literature Information
Yi-Lei Wang, Ya-Fan Zhao, Ai-Qin Wang, Tao Zhang, Jun Li
Understanding the geometry structures of gold clusters, especially with adsorbates, is essential for designing highly active gold nanocatalysts. Here, we report a detailed theoretical study of the geometry structures of bare and CO-saturated Aun+ (n = 4–6) clusters. It is found that the chemisorption of CO molecules leads to significant geometry changes of the gold clusters from two- to three-dimensions (3D), even for clusters as small as Au4+. These gold cationic clusters exhibit characteristic coordination binding sites that have distinct electronic structures. We also find that commonly used density functional theory (DFT) methods have difficulty in accurately predicting energies of some isomers of Aun+ clusters or Aun(CO)n+ complexes, with the calculated relative energies strongly depending on the exchange–correlation functionals used. Caution must be exercised when using DFT methods as a blackbox for predicting the structures and energies of gold clusters.
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